Desulfurization in hydrocarbon conversions



Jn. 21, 1947. J. G. ALLEN 2,414,626

DESULFURIZATION IN HYDROCARBON CONVERSIONS Filed Dec. 23.` 1944 ATTORNEYS ?atented Jan. 21, 1947 carica DESULFURIZATION IN HYDROCON CNVERSION S John Gordon Allen, Bartlesville, Okla-, assigner to Phillips PetroleumCompany, a corporation of Delaware Application December 23, 1944, Serial No. 569,594

This invention relates to the conversion and desulfurization of hydrocarbons. In one of the more particular aspects it relates to the alkylation and desulfurization of hydrocarbons in the presence of hydrogen fluoride and to the desulfurization and recycle of acid soluble oils which are formed during the process.

The use of hydrouoric'acid in hydrocarbon conversions is well known to the art. For example, it is used as a catalyst in organic reactions' involving` alkylation, isomerization, polymerization, cyclization," hydrofluorination and uorination. Perhaps the most important industrial process at the present time using hydrofluoric acid as catalyst is the alkylation of low-boiling hydrocarbons, such as isobutane and/or isopentane with propylene, various butylenes and/or various amylenes. to form valuable higher boiling compounds.

Such alkylation processes are`described, for instance, in Frey Patents 2,322 800, issued June 29, 1943, and 2,317,901, issued April 27, 1943, and also in an article by Frey in Chemical and Metallurgical Engineering, 1943, vol, 50, pages 12S to 128 (November, 1943). In such processes, the reactants are intimately mixed in the liquid phase at temperatures from 35 to 100 F. with liquid con centrated hydroiiuoric acid for reaction periods ranging from about 1 to 30 minutes, and the nlixture is passed to a settling zone in which a liquid hydrocarbon phase and aliquid acid phase are separated.

The hydrocarbon phase, which contains a substantial amount of hydrouoric acid, is 4withdrawn to a fractionatins tower from which an az'eotrope of acid and hydrocarbon is withdrawnoverhead and recycled to the reactor and/or setling zone. The heavier material which collects in the bottom of the azeotrope fractionator and which contains the desired alkylate product is passed through a tluorine removal zone, such as a bauxite treater, and is separated into fractions of the desired boiling ranges.

The lower, or acid, phase in the settling zone is withdrawn and recycled to the reactor, During the process of alkylation a relatively small amount of "acid-soluble oils are formed and remain dissolved in the acid phase ofthe separation. By acid soluble oils is meant those acid soluble hydrocarbon derivatives formed during the process of alkylation of low-boiling aliphatic hydrocarbons carried out in the presence of substantially anhydrous HF as a catalyst.' These oils, which may be formed at the rate of 1 to 2 or more percent of the alkylate produced, vary in 55 7 Claims. (Ci. 26d-683.4)

' in deleterious amounts.

composition but are unsaturated, consisting primarily ci' aromatic compounds with some oleflns, paraflns, and naphthenes. A typical example of these acid-soluble oils has the following charac'- teristics:

specific' gravity at 25 C. Refractive index (25 C.) Unsatura'tlon (cc. 1% bromine solution per cc.) 34.9 Fluorine, per cent by Weight 0.0013 Solubility in 98% H2804 80% Aniline point 35 C. 'Color Dark red to brown in transmitted light Initial boiling point `110 C. '70% distilled 425 C.

Processes for the separation of the acid and these acid-soluble oils have been described in/copending applications of Frey, Serial Number 429,961

iiled February 7, 1942, and Vinyard, Serial No. 545,415 led July 10, 1944.

The presence of certain proportions ci these acid soluble ols'durlng alkylation has been found to be desirable to effect desulfurization of the material in the reaction zone, to provide a better contact between the acid and the hydrocarbonV tion process outlined above, a substantial amount of sulfur and/or sulfur compounds is frequently introduced into the process by their presence in the feed stocks. Any appreciable quantity of sulfur in the feed stocks is usually transmitted to the-desirable fractions of the conversion eilluent Even a very small content of sulfur in gasolines may be responsible for bad odor;l corrosive properties, discoloration in lightflowering of octane number, and poor responseto tetraethyl lead. Thus, the maximum content by specification ofall grades of aviation gasoline is limited to 0.05 per cent land much lower concentrations are preferred. For the reasons given, then, it is vespecially desirable to keep the sulfur content of gasolines as low as possible.

It has now been found that an eiective control over the sulfur content of conversion products may be realized through the use oi' the acidsoluble oils described above in accordance with the present invention. Analyses of the cidsoluble oils recovered from the acid phase of the effluent from an'alkylation process as described 8 in which the mixture separates show that large amounts of the sulfur introduced into the reaction zone are'concentrated therein.

These oils, in addition to being soluble in hydroof the reaction products with the deleterious effects consistent with the sulfur content.

It is, therefore. an object of this invention to describe a process for the desulfurization of the products of a hydrocarbon conversion process,

Another object is to effect the desulfurization of hydrocarbons during a process of conversion.

Still another object is to effect desulfurization oi.' theA products of alkylation by means 'of acidsoluble oils.

A further object of this invention is to describe the desulfurization of alkylate by means of acidsoluble oils which are formed in the process, desulfurized and recycled to the process.

Other objects and advantages will be apparent to those skilled in the art from the disclosure and description which follow.

In one embodiment of the present invention,

I the acid-soluble oils and hydrofluoric acid in the` vacid phase from the settling zone of an alkylation process are separated by ash distillation and the acid-soluble oils are passed to a desu1 furization zone in which a substantial proportion of the sulfur is removed. The desulfurized oilsare added to the recycle acid stream in an amount sumcient to eiect a substantial reduction in sulfur concentration of the reaction' products and to maintain the desired composition of the light and heavy alkylate are separated. Unreacted isobutane is recycled to the reactor by line 2s Light gases are removed overhead by line- Il and light and heavy alkylates are removed by lines i8 and I9, respectively.

From the settling zone 8 the lower acid layer.A

whichmay contain as much as about 10 to 15 Der cent of hydrocarbon material and water. is.

withdrawn via line 2.0 and recycled to the reactor through line 6. A desired portion of the acid phase is passed through line 2i to a flash' tower 22 from Awhich substantially pure hydrogen iluoride is removed overhead by lines 23 andl recombined with recycle in line 6. If desired, the heavier material collectingin the bottom of the flash tower may be heated by means of heating coil 2lto distill oil more of the lighter compounds or stripped ofthese compounds by heated light gases. The heavier organic material collecting in the bottom of the tower comprises acidsoluble oils and water which, in accordance with this invention, are withdrawn via line 25 to a desulfurization` zone 26.v Desulfurization of the oils may be effected byany suitable means known" tothose versed in the art, suchas selective adsorption and/or selective absorption. Charcoal has been found satisfactory as an adsorbent in ing the reaction. The desulfurized oils are withmixed with an .olefincontaining fraction, suchas a butane-butylene mixture from line 4, so that the mol ratio of isobutane to oleilns is between drawn through line 9 to an azeotrope distilla` tion tower I Il. The overhead from distillation tower. I0 contains an azeotrop'ic mixture oi' acid and hydrocarbons, principally isobutane, which is recycled to the reactor by line II or to the acid settler through line I2. The bottoms from the azeotrope tower are withdrawn via line I3 to a treating zone I4. such as a tower containing bauxite, in which organic iluoride products and hydrogen iluoride entrained from the reaction zone are removed. The efiluent from the treater passes by line I5y into a fractionating zone I6 in which lightl gases, unreacted isobutane, and

drawn from the desulfurization zone by line 21 and passed to recycle with the acid in line 6. If desired all or a portion of the acid-soluble oils may be withdrawn from the system. before desulfurization by line 28. or after desulfurization by line 29. Y

`Various pumps, valves and other conventional equipment incidental to the operation of the system as described have been omitted from the diagram and description. These will'be apparent to one skilled in the art to which the invention pertains. Likewise, it is understood that reasonable care will be exercised in the selection and use of equipment constructed of material which is recognized to withstand corrosion in 1 that part of the system which is in contact with the acid, such las Monel and other metals listed in an article by C. M. Fehr, Materials of confur is introduced into thel reactor, the concentra-4 tion of sulfur in the` acid-soluble oils, which are concentrated in the acid phase from the settling zone, will be high. Also, in an operation in which the sulfur in the reaction zone vhas become excessive by reason of sulfur build-up through continuous recycle of untreated recycle acid, Athe concentration-of sulfur in the acid-soluble oils will be undesirably high.- In such cases, the amount of acid recycle withdrawn to the desuli furization zone may constitute a substantial p'ro'- portion 'ofthe recycle. i

1n addition to the effectiveness of havin'g an increased amount of sulfur-absorbent acid-soluble oil present in the reaction zone. is the desirability of having absorbent oil present throughout the entire length of the reaction time. Without the introduction of a desulfurizing agent. such as aci-'gozo sulfur-poor acid-soluble oils, .the desulfurization within the reaction zone would depend upon the action of these oils formed during the reaction. Such dependency involves a shorter contact time of the reactants and products with the absorbent oils 'and thus decreases the efciency of the desulfurization action. .An increased concentration of acid-soluble oils and longer residence time in the reaction zone assures better absorption and sulfur removal by theseoils. Furthermore, the introduction of the oils withthe acid recycle stream is advantageous since the oils are mutually soluble in the acid and in the hydrocarbon reactants, thereby producing a better contact between the two. A further advantage of the oils is. the control of acid concentration. Being solui ble in the acid, the oils. from the desulfurization step may be returned to the recycle acid stream in a suiilcient amount to serve as a vdiluent of the acid and establish-the desired concentration of acid for introduction into the reaction zone. I'he optimum anid concentration has been found to be between about 85 to 95 per cent for the alkylation process above. Examination of a, few preliminary test operations will determine the optimum conditions of acid concentration, the most desirable amount of recyclev acid to withdraw for further treatment, and other factors for the alkylation of other hydrocarbons.

The advantages of this invention are demonstrated by the following specific example of hydroiluoric acid alkylation: A butene-amylene feed, containing 32.6 per cent olefinic material and 0.009 per cent sulfur, was admixedwith a 96 per cent isobutanestock containing 0.001 per cent sulfur in an isobutane-to-oleiln ratio of 6.96 to 1.

Hydroiluoric acid of 88.5 per cent concentration was introduced into the mixing zone at an acidto-hydrocarbon ratio of 0.95 to 1. After a contact time of 35- minutes, the mixture was withthe bottom ofthe fractionator was removed,

passed through bauxite treaters for the extraction of iluorine compounds and of some sulfur compounds, and. fractionated into light and heavy alkylate and other fractions. 'I'he acid layer was withdrawn from the settler and recycled to the reactor. Five per 'cent of the acid recycle stream was by-passed to the acid flash .tower from which .a 95 per cent hydrofluoric acid vapor was removed overhead and added to the main stream of recycle acid. Acid-soluble oils and water were removed from the bottom of the flash tower and passed to the desulfurization zone. In this zone the oils were subjected to treatment with an aqueous'alkaline solution of litharge, separated therefrom by stratification, and passed through a tower- 6 y After dehydration and desulfurization, the acidsoluble oils 'were then recycled to the reactor.

Of the 47.7 pounds per day of sulfur introduced into the system through the hydrocarbon feed. about 60 per cent was accounted for in the fractionsirom the iinal fractionation of the hydrocarbon phase and in the acid-soluble oils from the flash tower. A large portion of the balance of the sulfur was removed by the bauxite treater following the azeotropic fracticnator and a small amount of sulfur was recycled in the untreated acid recycle. The acid-soluble oils contained 38 per cent of the total sulfur introducedI in the system and the desired light alkylate fraction contained 13.3 per cent. which represented a concentration in this fraction of 0.0021 per cent. In this example the concentration of the acid-soluble oils was about 2 per cent of the acid and the concentration of sulfur in these oils amounted to about l1 per cent so that the sulfur in the system v was about 0.02 per cent by weight of the acid.

Another portion of the same feed was treated under identical conditions without the supplemental treatment of a part of the recycle acid stream. In this operation all of the acid phase from the settling zone vwas recycled directly to the reactor. The sulfur concentration in the desired light allqflate fraction increased to 0.0034 per cent by weight of this fraction. orI an increase in concentration of more than 60 per cent over that in the preceding method. 'The sulfur content of the system in this example was approximately 0.06 per cent by weight of the acid.

A comparison of the results obtained by the two methods of procedure just described clearly indicates the advantages ofwithdrawal and further treatment of at least a portion of the recycle acid stream and the acid-solubleoils contained therein. For example, withdrawal and treatment of the tive per cent of recycle acid,v in

Vthe example reduced the sulfur content of the systems sufficiently to substantially lower the sulfur content of the desired fractions.

In the event the sulfur in the system begins to'exceed the concentration allowable for satisfactory operation as evidenced inthe transmission and increase of sulfur lin the desirable Valkylate fractions. larger amounts of acid-soluble oils may be recovered and desulfurize'd to reduce the sulfur content of the system. In the above examples, a concentration ,of sulfur between 0.02 and 0.06 per cent by weight of-the acid results in a very low concentration of sulfur in the light alkylate fraction of the product,- the higher value of 0.06 per cent effecting a concentration in the desired `fraction of only about 0.003 per cent per cent, the concentration of'the `acid-soluble oils should not exceed about 110 per cent of the j acid feed. Since about 1 to 2 per cent of acid soluble oils are formed in the conversion, this value may represent a satisfactory minimum conj Y per cent ofthe acid.

of adsorptive charcoal which adsorbs the sulfide compounds and a, tower containing calcined bauxite to absorb moisture and dehydrate the oils.

while the invention hasebeen'described in connection -with a process of' alkylation employing f produced and recycled to the same process, it is not intended to limit the scope of the invention to such a process. vIf desired, these oils from one unit of hydrocarbon conversion in which an excess is being produced may be transferred'to another changes may be made without departing from the spirit of the invention and the nscope of the following claims. l

I claim: l. In a process for the alkylation of hydrocarbons containing organic sulfur compounds in the presence of hydroiluoric acid catalyst, the improvement of addingacid-soluble oils which are formed. during conversion of hydrocarbons in the presence of said `h'ydroiluoric acid to the reactants in the reaction zone, separating said oils containing absorbed sulfur compounds from the ei'liuent, desulfurizing at least a portion of` said acidsoluble oils, andlrecycling said desulfurized oils to the reaction zone as the acid-soluble oils added thereto.

2. A process for theI alkylation of parafilns with olens which comprises reacting :said parafllns and olens in the presence of hydrouorlc acid, forming acid-soluble oils during the reaction, separating the acidhaving acid-soluble oils dissolved therein from the hydrocarbon eilluent, recycling a v portion of the separated acid to the reaction zone, treating a portion of the separated acid to recover acid-soluble oils therefrom, desulfurizing said acid-soluble oils, and recycling saiddesulfurizedA oils to the reaction zone to selectively absorb. organic `sulfur compounds in said parailns and oleflns.

3. A process for the alkylation of an isoparaillnolefin mixture containing sulfur compoundsas impurities which comprises contacting said isoparailln-olefln mixture with hydrofiuoric acid under alkylation conditions, forming an alkylate phase and an acid phase having acid-soluble oils dissolved therein, separating said alkylate from saidacid phase, recovering acid-soluble oils from said acid phase, said acid-soluble oils having sulfur compounds selectively dissolved therein, desul-` furizins atleast a portion of said acid-soluble oils 'to reduce the sulfur content thereof, and recycling at least a portion of said desulfurized acid-soluble oils to said alkylation zone to selectively dissolve sulfur compounds therein.

4. In a process for the alkylation of low boiling isoparamns with olens'in the presence of concentrated hydroiluoric acid as a catalyst, wherein the hydrocarbon reactants contain sulfur compounds as impurities therein, wherein acidsoluble oils are formed during the alkylation, and wherein the reaction mixture is separated into an acid phase and a hydrocarbon phase andthe acid phase is recycled to the reaction zone, the

method of. removing sulfur from the system which comprises separating at least a portion of the acid soluble oils from the acid phase prior to its recycle to the reaction zone, desulfurizing said separated acidsoluble oil, and returning said desulfurized acid-soluble oil to said. reaction zone.

5. A process according to claim 4 in which a predetermined maximum sulfur content in the alkylate produced is maintained by desulfurizingy apredeterrnined proportion ,of the acid-soluble oils produced sufllcient to remove'the necessary amount of sulfur from the system, and in which a predetermined concentration of acid-soluble oil is maintained in the reaction zone by removing a portion of the acid-soluble oil from the system. ff

6. In a process for the alkylation of hydrocarbons containing organic sulfur compounds in theJ presence of hydrouoric' acid catalyst, the improvement of adding acid-soluble oils which are formed during conversion of hydrocarbons in the presence of said hydrofluoric acid to the reactants in the reaction zone, separating said oils containing absorbed sulfur compounds from the f eiliuel'it, desulfurizing at least a portion "of said acid-soluble oils, and recycling said desulfurized oils to the reaction zone as at least a portion of the acid-soluble oils added thereto.

7. A process for the desulfurization of yhydrocarbons containing organic sulfur compoundsJ moval of said sulfur compounds and recycling the desulfurized acid-soluble oils for the selective extraction of sulfur compounds.

JOHN GORDON ALLEN. 

